Methods and systems for generating polyols
View Patent ↗Disclosed are methods for generating propylene glycol, ethylene glycol and other polyols, diols, ketones, aldehydes, carboxylic acids and alcohols from biomass using hydrogen produced from the biomass. The methods involve reacting a portion of an aqueous stream of a biomass feedstock solution over a catalyst under aqueous phase reforming conditions to produce hydrogen, and then reacting the hydrogen and the aqueous feedstock solution over a catalyst to produce propylene glycol, ethylene glycol and the other polyols, diols, ketones, aldehydes, carboxylic acids and alcohols. The disclosed methods can be run at lower temperatures and pressures, and allows for the production of oxygenated hydrocarbons without the need for hydrogen from an external source.
1. A method of generating alcohols and ketones from a biomass-derived oxygenated hydrocarbon, the method comprising:
a. providing an aqueous feedstock solution comprising water and at least one biomass-derived, water-soluble oxygenated hydrocarbon having two or more carbon atoms;
b. providing hydrogen;
c. catalytically reacting the biomass-derived, water-soluble oxygenated hydrocarbon with the hydrogen in the presence of a catalyst comprising a first metal and a distinct second metal, the first metal selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ir, and Ru, and the second metal selected from the group consisting of Ni, Pd, Co, Ru, Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, and Sn, at a temperature and a pressure to produce a reaction product comprising mono-oxygenated alcohols and mono-oxygenated ketones.
2. The method of claim 1 wherein the catalyst further comprises a distinct third metal selected from the group consisting of Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, Sn, V, and Ta.
3. The method of claim 2 wherein the catalyst further comprises a distinct fourth metal selected from the group consisting of Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, Sn, V, and Ta.
4. The method of claim 2 wherein the catalyst further comprises a support.
5. The method of claim 4 wherein the support is selected from the group consisting of tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, phosphated alumina, heteropolyacids, and mixtures thereof.
6. The method of claim 1 wherein the hydrogen reacts with the biomass-derived, water-soluble oxygenated hydrocarbon at a temperature between about 100° C. and 300° C. and a pressure between about 72 psig and 1300 psig.
7. The method of claim 1 wherein the hydrogen comprises at least one of an external hydrogen, in-situ generated hydrogen, or recycled hydrogen.
8. The method of claim 1 wherein the biomass-derived, water-soluble oxygenated hydrocarbon comprises a member selected from the group consisting of a lignocellulose derivative, a cellulose derivative, a hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol, and a polyol.
9. The method of claim 1 wherein the reaction product further comprises unreacted oxygenated hydrocarbons.
10. The method of claim 9 wherein the unreacted oxygenated hydrocarbons are recycled and combined with the aqueous feedstock stream.
11. A method of generating a mono-oxygenated compound, the method comprising reacting a biomass-derived, water-soluble oxygenated hydrocarbon with hydrogen over a catalyst at a temperature between about 100° C. and 300° C., a pressure between about 72 psig and 1300 psig and a WHSV between about 0.5 and 5.0 grams of oxygenated hydrocarbon per hour, to produce a reaction product comprising mono-oxygenated alcohols and mono-oxygenated ketones, wherein the catalyst comprises a first metal and a distinct second metal, the first metal selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ir, and Ru, and the second metal selected from the group consisting of Ni, Pd, Co, Ru, Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, and Sn.
12. The method of claim 11 wherein the catalyst further comprises a distinct third metal selected from the group consisting of Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, Sn, V, and Ta.
13. The method of claim 12 wherein the catalyst further comprises a distinct fourth metal selected from the group consisting of Cu, Fe, Co, Zn, Cd, Au, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, Sn, V, and Ta.
14. The method of claim 11 wherein the catalyst further comprises a support.
15. The method of claim 14 wherein the support is selected from the group consisting of tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, phosphated alumina, heteropolyacids, and mixtures thereof.
16. The method of claim 11 wherein the hydrogen comprises at least one of an external hydrogen, in-situ generated hydrogen, or recycled hydrogen.
17. The method of claim 11 wherein the biomass-derived, water-soluble oxygenated hydrocarbon comprises a member selected from the group consisting of a lignocellulose derivative, a cellulose derivative, a hemicellulose derivative, a carbohydrate, a starch, a monosaccharide, a disaccharide, a polysaccharide, a sugar, a sugar alcohol, an alditol, and a polyol.
18. The method of claim 11 wherein the reaction product further comprises unreacted oxygenated hydrocarbons.
19. The method of claim 18 wherein the unreacted oxygenated hydrocarbons are recycled and combined with the biomass-derived, water-soluble oxygenated hydrocarbon.
20. A method of generating a mono-oxygenated compound, the method comprising reacting a biomass-derived, water-soluble oxygenated hydrocarbon with hydrogen over a catalyst at a temperature, a pressure, and a WHSV sufficient to produce a reaction product comprising mono-oxygenated alcohols and mono-oxygenated ketones, and wherein the catalyst comprises a first metal selected from the group consisting of Ni, Pd, Ru, and Co, a distinct second metal selected from the group consisting of Cu, Fe, Co, Zn, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, and Sn, a distinct third metal different than the first metal and the second metal and selected from the group consisting of Cu, Fe, Co, Zn, Ag, Nb, Zr, Ti, Ge, Re, Mn, Cr, Mo, W, Sn, V, and Ta, and a support selected from the group consisting of tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, phosphated alumina, heteropolyacids, and mixtures thereof.